One- and Two-Photon Photochemistry and Photophysics of Poly(arylenevinylene)s Containing a Biphenyl Moiety

Authors

  • Veronika Strehmel Dr.,

    1. University of Potsdam, Institute of Chemistry, Interdisciplinary Research Center for Biopolymers, Karl Liebknecht Str. 24/25, 14476 Potsdam-Golm, Germany, Fax: (+49) 331-977-5036
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  • Ananda M. Sarker Dr.,

    1. University of Massachusetts at Amherst, Department of Polymer Science and Engineering, Department of Chemistry, Amherst, MA01003, USA
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  • Paul M. Lahti Prof. Dr.,

    1. University of Massachusetts at Amherst, Department of Polymer Science and Engineering, Department of Chemistry, Amherst, MA01003, USA
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  • Frank E. Karasz Prof. Dr.,

    1. University of Massachusetts at Amherst, Department of Polymer Science and Engineering, Department of Chemistry, Amherst, MA01003, USA
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  • Matthias Heydenreich Dr.,

    1. University of Potsdam, Institute of Chemistry, Interdisciplinary Research Center for Biopolymers, Karl Liebknecht Str. 24/25, 14476 Potsdam-Golm, Germany, Fax: (+49) 331-977-5036
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  • Hendrik Wetzel Dr.,

    1. Fraunhofer Institute for Applied Polymer Research, Geiselbergstr. 69, 14476 Potsdam-Golm, Germany
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  • Sophie Haebel Dr.,

    1. University of Potsdam, Institute of Chemistry, Interdisciplinary Research Center for Biopolymers, Karl Liebknecht Str. 24/25, 14476 Potsdam-Golm, Germany, Fax: (+49) 331-977-5036
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  • Bernd Strehmel Priv.-Doz. Dr.

    1. University of Potsdam, Institute of Chemistry, Interdisciplinary Research Center for Biopolymers, Karl Liebknecht Str. 24/25, 14476 Potsdam-Golm, Germany, Fax: (+49) 331-977-5036
    2. Kodak Polychrome Graphics, Research and Development, An der Bahn 80, 37520 Osterode am Harz, Germany, Fax: (+49) 5522-997-577
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Abstract

Photochemical and photophysical properties were investigated for poly(arylenevinylene)s containing a flexible biphenyl “hinge” unit by applying one-photon (OP) and two-photon (TP) excitation to explore excited-state properties. The poly(arylenevinylene)s were poly[(2,5-dihexyloxy-p-phenylenevinylene)-alt-(4,4′-dihexyloxy-3,3′-biphenylenevinylene)] (1), poly[(2,5-dihexyloxy-p-phenylenevinylene)-alt-(2,2′-dihexyloxy-3,3′-biphenylenevinylene)] (2), and poly[(2,5-dihexyloxy-p-phenylenevinylene)-alt-(2,2′-biphenylenevinylene)] (3). Effective emission quantum yields and related photonic properties were evaluated on a realistic per-chromophore basis using effective conjugation lengths based on the Strickler–Berg relationship. Intramolecular photocyclization was deduced to occur in the one case where the biphenyl molecular connectivity permitted the reaction, based on matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF), heteronuclear multiple-quantum coherence (HMQC)-NMR, and gel-permeation chromatography (GPC) results. The various photoprocesses could be induced by either OP or TP excitation, though the first excited singlet state is the photoactive state. The higher excitation energy of the TP excited state favors indirect population of the S1 state by electronic coupling between the TP and OP excited states [λequation image (nm): 726; δ (GM)9: 1=229, 2=215, 3=109). Photochemical processes occurring from the lowest OP excited state (S1) could therefore also be indirectly induced by TP excitation.

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